Aminoarylsulfonic acid-phenol-formaldehyde condensate and concrete admixture comprising the same

ABSTRACT

The present invention relates to aminoarylsulfonic acid-phenol-formaldehyde condensate and concrete admixture comprising the same for incorporation in cementing compositions, for example, mortar, cement paste and the like, for improving slumping characteristics.

This is a division, of application Ser. No. 07/436,953 now U.S. Pat. No.4,936,918, filed on Nov. 15, 1989, which was a continuation of Ser. No.07/248,103, filed on Sept. 23, 1988, now abandoned.

The present invention relates to aminoarylsulfonicacid-phenol-formaldehyde condensate (hereinafter referred to as ASPFC)and concrete admixture comprising the same for incorporation incementing composition, for example, concrete, mortar, cement paste andthe like, that is, an inorganic hydraulic cement containing composition.

The concrete admixture which comprises ASPFC mentioned below improvesconsistency of fresh cementing composition, and further restrains thechange of the fluidity such as slump loss with the passage of time.

More definitely, when the concrete admixture of this invention is addedto the cementing composition, the slump of the cementing composition canbe increased without adding water and the cementing composition can betransported without slump loss for a long period of time, and furtherthis concrete admixture facilitates flow rates of fresh cementingcomposition when the fresh cementing composition is pumped to a desiredlocation during cementing operation.

ASPFC is a condensate prepared by polymerizing 20 to 70 parts by weightof a compound of the general formula:

    R.sup.1 SO.sub.3 H                                         (I)

wherein R¹ is ##STR1## (wherein R_(a) ¹ is hydrogen or lower alkyl) or##STR2## or its salt, 10 to 50 parts by weight of a compound of thegeneral formula: ##STR3## wherein R² is hydrogen, lower alkyl, loweralkoxy, hydroxy or carboxy, or its salt, and 10 to 40 parts by weight offormaldehyde.

Since ASPFC of the present invention reduces apparently the viscosity offresh cementing composition to which it is added, it is possible toreduce the unit water content of fresh cementing composition whichresults in greater compressive strength in the hardened concrete asobtained.

Up to now, although various kinds of concrete admixture are known in theart, they are insufficient in improvement of consistency of freshcementing composition and in restraining of the change of the fluiditysuch as slump loss with the passage of time.

The inventors of the present invention have conducted the research workto find out more preferable concrete admixture which possesses improvedcharacteristics in consistency and restraining of the change of fluiditysuch as slump loss with the passage of time, and have completed thepresent invention.

In the above and subsequent descriptions of the present specification,the various definitions which the present invention intends to includewithin the scope thereof are explained in detail as follows.

The term "lower" is used to intend a group having 1 to 6 carbon atom(s),unless otherwise provided.

Suitable "lower alkyl" may include straight or branched one, having 1 to6 carbon atom(s), such as methyl, ethyl, propyl, isopropyl, butyl,t-butyl, pentyl, hexyl and the like.

Suitable "lower alkoxy" may include straight or branched one such asmethoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy,isopentyloxy, hexyloxy and the like.

ASPFC can be prepared by polymerizing 20 to 70 parts by weight of acompound (I), 10 to 50 parts by weight of a compound (II) and 10 to 40parts by weight of formaldehyde in an aqueous condition under warming orheating.

Now, in order to show the utility of ASPFC of the present invention, thetest data of the representative ASPFCs on mortar and concrete are shownin the following.

TEST 1 Mortar slump test

(1) Test Method

Consistency was measured by mortar slump test at 20° C, and slump of themortars containing the test compounds was compared with that of thereference mortar (non-additive).

Materials and the mortar composition utilized in the test were 700 g ofordinary Portland cement specified in JIS R 5210, 1960 g of river sand(specific gravity: 2.63, fineness modulus: 2.66) and 339.5 ml of wateror an aqueous solution containing 2.8 g of the test compound.

The mortars were made by mechanical mixing of ingredients according tothe standard method in JIS R 5201.

Mortar slump was determined in accordance with JIS A 1101 by using aslump corn of half size of the standard mold (with base 100 mm indiameter, top 50 mm in diameter and the height 150 mm).

Air content of the test mortar was measured by gravimetric method.

After initial measurement of the slump and air content, the mortar wasrecovered into the mixing bowl, allowed to stand for 60 minutes and thenremixed by using mixing spoon in the bowl.

The slump and air content was measured again, as described above.

(2) Test Results

The test results are given in Table 1.

                  TABLE 1                                                         ______________________________________                                        Test compounds                                                                             Slump (cm)   Air content (%)                                     (Example Nos.)                                                                             0 min.  60 min.   0 min.                                                                              60 min.                                  ______________________________________                                        1            9.6     8.5       2.7   2.2                                      2            10.2    7.4       2.2   1.8                                      3            9.3     7.4       4.1   3.1                                      4            10.7    7.9       2.8   1.1                                      5            9.3     6.3       2.4   2.1                                      6            8.2     5.5       2.5   1.6                                      7            9.9     6.9       2.2   2.1                                      8            8.5     5.6       3.0   2.3                                      9            10.6    8.8       1.5   1.6                                      10           8.8     6.3       2.4   1.9                                      11           10.6    8.5       2.2   1.7                                      12           10.2    7.8       1.6   1.1                                      13           11.0    8.9       2.1   1.3                                      14           9.7     6.8       2.3   1.7                                      15           10.6    10.8      1.8   1.0                                      16           11.2    9.9       1.5   1.0                                      17           11.3    10.2      1.0   0.8                                      18           10.7    10.8      2.0   1.0                                      19           11.4    8.5       1.6   2.0                                      20           9.9     9.1       3.5   2.3                                      21           9.4     9.7       3.2   2.0                                      22           11.0    10.8      2.2   1.4                                      23           11.4    9.7       1.1   0.9                                      24           10.3    7.9       0.7   0.9                                      25           10.3    7.4       0.5   0.7                                      26           11.6    8.8       1.2   1.5                                      27           10.9    6.9       1.5   2.9                                      28           8.3     4.8       3.5   2.7                                      29           8.7     5.1       10.9  6.1                                      30           9.7     6.2       4.0   2.8                                      31           11.7    10.5      1.0   1.6                                      32           12.6    11.6      0.3   0.1                                      33           12.0    10.6      1.2   1.0                                      34           9.7     7.7       2.9   1.9                                      35           10.2    8.0       2.0   1.2                                      36           11.8    9.2       0.2   0.6                                      37           6.8     3.0       3.8   3.1                                      38           7.4     5.4       2.0   2.6                                      39           7.2     3.2       4.0   3.0                                      Reference    3.5     --        2.7   --                                       (non-additive)                                                                ______________________________________                                    

TEST 2 Concrete test

(1) Test Method

Consistency of the concrete containing test compounds were compared withthat of the plain concrete (non-additive), and slump loss (thetime-dependent change of fluidity) of the concrete was compared withthat of the reference concrete adjusted to the same initial slump byincreasing unit water content. The method utilized in the test was thebasic procedure described in the Japan Industrial Standard (JIS) A 6204for chemical admixtures for concrete.

Materials utilized in the test were as follows:

Cement: a mixture of ordinary Portland cements specified in JIS R 5210from three different manufacturers.

Fine aggregate: river sand

specific gravity: 2.64

modulus: 2.75

Coarse aggregate: crushed stone

specific gravity: 2.67

fineness modulus: 6.70

Mix proportions of concrete are shown in Table 2.

The concrete was prepared by mixing cement, aggregates and water orwater containing a test compound in a forced mixing type mixer for 1.5minutes on a scale of 30 liters, and was allowed to stand in a mixingplate.

Initial slump and the time-dependent change of slump (at every 30minutes intervals to 1.5 hours) were measured after remixing in themixing plate.

(2) Test Results

The results are given in Table 3.

                  TABLE 2                                                         ______________________________________                                        Mix proportions of concrete                                                           Water-cement                                                                           s/a     Unit weight (kg/m.sup.3)                             Concrete  ratio (%)  (%)     W    C    S    G                                 ______________________________________                                        Plain and test                                                                          58.1       49      186  320  909  957                               concrete                                                                      Reference 66.3       49      212  320  875  921                               concrete                                                                      ______________________________________                                         W: water, C: cement, S: sand, G: coarse aggregate                             s/a: ratio of sand to aggregates (aggregates contain sand and coarse          aggregate)                                                               

                                      TABLE 3                                     __________________________________________________________________________                 Dosage                                                                        of the test                                                                            Air                                                                  compounds [%                                                                           content                                                                           Slump (cm)                                          Concrete     (w/w) of cement]                                                                       (%) 0  30 60 90 minutes                                 __________________________________________________________________________    Plain concrete                                                                             --       1.2 8.0                                                 Test concrete containing                                                      a compound of Example 16                                                                   0.4      0.7 20.5                                                                             20.0                                                                             20.0                                                                             19.5                                       a compound of Example 20                                                                   0.4      1.3 21.0                                                                             20.0                                                                             20.0                                                                             20.0                                       a compound of Example 31                                                                   0.4      1.2 20.5                                                                             20.5                                                                             20.5                                                                             19.5                                       Reference concrete                                                                         --       0.8 20.5                                                                             17.5                                                                             15.5                                                                             14.0                                       __________________________________________________________________________

As clear from the test results as stated above, ASPFC of the presentinvention improves consistency of cementing composition (cf. highinitial slump) and restrains the slump loss with the passage of time inconcrete as compared with the reference.

It might be clear from the test results shown in Table 3 that ASPFC muchreduced unit water content without air-entraining.

Concrete having good fluidity can be prepared by admixing ASPFC (0.01 to1.0% of cement, preferably 0.1 to 0.6% of cement) with the ordinaryconcrete.

Said ordinary concrete may include cement (5-25%), coarse aggregate(30-60%), fine aggregate (20-50%), water (4-10%), and air entrainingagent (0-1% of cement) and/or water-reducing agent (0-1% of cement).

Mortar having good fluidity can be prepared by admixing ASPFC (0.01 to1.0% of cement, preferably 0.1 to 0.6% of cement) with the ordinarymortar.

Said ordinary mortar may include cement (15-45%), water (5-30%), sand(35-75%), and air entraining agent (0-1% of cement) and/orwater-reducing agent (0-1% of cement).

Cement paste having good fluidity can also be prepared by admixing ASPFC(0.01 to 1.0% of cement, preferably 0.1 to 0.6% of cement) with theordinary cement paste.

Said ordinary cement paste may include cement (20-80%) and water(80-20%).

As the cement, there may be mentioned cement currently on the market,such as ordinary portland cement, high-early-strength cement, moderateheat cement, blast-furnace slag cement and fly ash cement, with fly ash,granulated slag powder, siliceous admixtures and the like.

The following Examples are given for the purpose of illustrating thepreparation of ASPFC of the present invention.

EXAMPLE 1

To a mixture of 4-aminobenzenesulfonic acid (8.66 g) and phenol (4.70 g)in water (30 ml) was added 20% aqueous sodium hydroxide (10.20 g) andthe resulting solution was adjusted to pH 8.1 with 0.1N aqueous sodiumhydroxide. A weight of the solution was adjusted to 56.00 g with waterand then heated To the solution was added 37% aqueous formaldehyde (8.10g) under refluxing and the reaction mixture was stirred for 7.5 hoursunder refluxing. The solution was cooled to room temperature, adjustedto pH 11.0 with 20% aqueous sodium hydroxide (3.26 g) and condensed at40° C. to afford an aqueous solution of the condensate (49.40 g).

Ratio (4-aminobenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water) 1:2.49

Viscosity of the aqueous solution of the condensate: 8.9 (cP at 25° C.,30%)

Molecular weight Mw: 1976, Mn: 833

Examples 2 to 14 was conducted in a similar manner to that of Example 1.

    __________________________________________________________________________    Stating monomers                          Resulting condensate                Example                                                                            Ratio (4-aminobenzenesulfonic                                                                Ratio (starting                                                                        Polymerizing conditions                                                                         Molecular weight               No.  acid:phenol:formaldehyde)                                                                    monomers:water)                                                                        Initial pH                                                                          Reaction time                                                                        Viscosity                                                                          Mw   Mn                        __________________________________________________________________________    2    1:1:2          1:2.49   8.3   7.5    9.4                                 3    1:1:2          1:2.49   7.9   7.5    10.3                                4    1:1:2          1:2.21   8.1   7.5    10.3                                5    1:1:2          1:2.49   8.1   7.0    10.1                                6    1.1:0.9:2      1:2.47   8.1   7.5    8.9                                 7    0.9:1.1:2      1:2.51   8.1   7.5    10.4                                8    1.2:0.8:2      1:2.45   8.1   7.5    8.2                                 9    1:1:2          1:2.49   8.5   7.5    8.8                                 10   1:1:2          1:2.49   7.7   7.5    10.6                                11   1:1:2.1        1:2.48   8.1   7.5    10.0                                12   1:1:2.2        1:2.47   8.1   7.5    9.8                                 13   1:1:3          1:2.36   8.1   7.5    9.1  3264 1957                      14   1:1:2          1:1.94   8.1   7.5    10.6                                __________________________________________________________________________     Molecular weight was obtained using gel permeation method.                    Mw: weight average molecular weight, Mn: number average molecular weight      Standard: sodium polystylene sulfonate                                        Viscosity: The viscosity of the solution was measured with a VISCONIC ED      type viscometer (made by TOKYO KEIKI CO., LTD), cP at 25° C., 30% 

EXAMPLE 15

To a mixture of 4-aminobenzenesulfonic acid (594.8 g) and phenol (323.2g) in water (2000.0 ml) was added 20% aqueous sodium hydroxide (704.0 g)and the resulting solution was adjusted to pH 8.1 with 0.1N aqueoussodium hydroxide. The weight of the solution was adjusted to 3850.0 gwith water and then heated. To the solution was added 37% aqueousformaldehyde (557.4 g) under refluxing and the reaction mixture wasstirred for 7.5 hours under refluxing (1st step). The mixture was cooledto room temperature, adjusted to pH 11.0 with 20% aqueous sodiumhydroxide (252.5 g) and refluxed for 3 hours (2nd step) to afford anaqueous solution of the condensate (4659.9 g).

Ratio (4-aminobenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.49

Molecular weight: Mw: 4336, Mn: 943

Examples 16 to 23 was conducted in a similar manner to that of Example15.

    __________________________________________________________________________                                  Polymerizing conditions                         Stating monomers              1st step 2nd step Resulting condensate          Example                                                                            Ratio (4-aminobenzenesulfonic                                                                 Ratio (starting                                                                        Initial                                                                           Reaction                                                                           Initial                                                                           Reaction   Molecular weight        No.  acid:phenol:formaldehyde)                                                                     monomers:water)                                                                        pH  time pH  time Viscosity                                                                           Mw   Mn                 __________________________________________________________________________    16   1:1:2           1:2.49   8.1 7.5  10.0                                                                              1.0  3.7 *1                        17   1:1:2           1:2.49   8.1 7.5  10.0                                                                              3.0  3.7 *1                                                                              3775 1000               18   1:1:2           1:2.49   8.1 7.5  11.0                                                                              1.0  3.9 *2                                                                              2760 899                19   1:1:2           1:2.56   8.1 7.5  11.0                                                                              3.0                                20   1:1:2           1:2.49   8.1 7.5  12.0                                                                              1.0        1920 737                21   1:1:2           1:2.49   8.1 7.5  12.0                                                                              3.0        2034 696                22   1:1:2           1:2.49   8.1 7.5  11.0                                                                              5.0                                23   1:1:2           1:2.49   8.1 7.5  10.0                                                                              5.0                                __________________________________________________________________________     Viscosity: *1: at 25° C., 22.3%; *2: at 25° C., 21.5%      

EXAMPLE 24

To a mixture of 4-aminobenzenesulfonic acid (17.32 g) and pyrocatechol(11.01 g) in water (60 ml) was added 20% aqueous sodium hydroxide (21.12g) and the resulting solution was adjusted to pH 8.1 with 0.1N aqueoussodium hydroxide. The weight of the solution was adjusted to 119.20 gwith water and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 7.5 hours under refluxing. Further, 37% aqueous formaldehyde(8.12 g) was added thereto under refluxing and stirred for 7.5 hoursunder refluxing (1st step). The mixture was cooled to room temperature,adjusted to pH 11.0 with 20% aqueous sodium hydroxide (7.72 g) andrefluxed for 3 hours (2nd step) to afford an aqueous solution of thecondensate (151.30 g).

Ratio (4-aminobenzenesulfonic acid:pyrocatechol: formaldehyde): 1:1:3

Ratio (starting monomers:water): 1:2.45

Viscosity of the aqueous solution of the condensate: 36.3 (cP at 25° C.,30%)

Molecular weight: Mw: 5832

EXAMPLE 25

To a mixture of 4-aminobenzenesulfonic acid (34.64 g) and hydroquinone(22.02 g) in water (122 ml) was added 20% aqueous sodium hydroxide(40.92 g) and the mixture was stirred at 50° C. The resulting solutionwas adjusted to pH 8.03 with 0.1N aqueous sodium hydroxide. The weightof the solution was adjusted to 238.40 g with water and then heated. Tothe solution was added 37% aqueous formaldehyde (32.46 g) underrefluxing and the reaction mixture was stirred for 7.5 hours underrefluxing (1st step). The mixture was cooled to room temperature,adjusted to pH 11.0 with 20% aqueous sodium hydroxide (25.04 g) andrefluxed for 3 hours (2nd step) to afford an aqueous solution of thecondensate (295.90 g).

Ratio (4-aminobenzenesulfonic acid:hydroquinone: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.52

Viscosity of the aqueous solution of the condensate: 23.9 (cP at 25° C.,30%)

Molecular weight: Mw: 4895

EXAMPLE 26

To a mixture of 3-aminobenzenesulfonic acid (17.32 g) and phenol (9.41g) in water (55 ml) was added 20% aqueous sodium hydroxide (20.41 g) andthe resulting solution was adjusted to pH 8.1 with 0.1N aqueous sodiumhydroxide. The weight of the solution was adjusted to 112.10 g withwater and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 9.25 hours under refluxing (1st step). The mixture wascooled to room temperature, adjusted to pH 11.0 with 20% aqueous sodiumhydroxide (5.14 g) and refluxed for 3 hours (2nd step) to afford anaqueous solution of the condensate (133.50 g).

Ratio (3-aminobenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.49

Molecular weight: Mw: 4891, Mn: 1091

EXAMPLE 27

To a mixture of 2-aminobenzenesulfonic acid (17.32 g) and phenol (9.41g) in water (54 ml) was added 20% aqueous sodium hydroxide (20.39 g) andthe resulting solution was adjusted to pH 8.1 with 0.1N aqueous sodiumhydroxide. The weight of the solution was adjusted to 112.10 g withwater and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 9.25 hours under refluxing (1st step). The mixture wascooled to room temperature, adjusted to pH 11.0 with 20% aqueous sodiumhydroxide (5.26 g) and refluxed for 3 hours (2nd step) to afford anaqueous solution of the condensate (133.60 g).

Ratio (2-aminobenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.49

Molecular weight: Mw: 5078, Mn: 1180

EXAMPLE 28

To a mixture of 2-aminobenzenesulfonic acid (17.32 g) and m-cresol(10.83 g) in water (63 ml) was added 20% aqueous sodium hydroxide (20.30g) and the resulting solution was adjusted to pH 8.1 with 0.1N aqueoussodium hydroxide. The weight of the solution was adjusted to 118.30 gwith water and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 7.5 hours under refluxing (1st step). The mixture was cooledto room temperature, adjusted to pH 11.0 with 20% aqueous sodiumhydroxide (3.08 g) and refluxed for 1 hour (2nd step) to afford anaqueous solution of the condensate (137.60 g).

Ratio (2-aminobenzenesulfonic acid:m-cresol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.52

Viscosity of the aqueous solution of the condensate: 82.8 (cP at 25° C.,30%)

EXAMPLE 29

To a mixture of 2-amino-5-methylbenzenesulfonic acid (18.72 g) andphenol (9.41 g) in water (61 ml) was added 20% aqueous sodium hydroxide(20.00 g) and the mixture was stirred at 50° C. The resulting solutionwas adjusted to pH 7.92 with 0.1N aqueous sodium hydroxide. The weightof the solution was adjusted to 118.30 g with water and then heated. Tothe solution was added 37% aqueous formaldehyde (16.23 g) underrefluxing and the reaction mixture was stirred for 7.5 hours underrefluxing (1st step). The mixture was cooled to room temperature,adjusted to pH 11.0 with 20% aqueous sodium hydroxide (8.40 g) andrefluxed for 1 hour (2nd step) to afford an aqueous solution of thecondensate (142.90 g).

Ratio (2-amino-5-methylbenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.53

Viscosity of the aqueous solution of the condensate: 13.8 (cP at 25° C.,30%)

Molecular weight: Mw: 11870

EXAMPLE 30

To a mixture of 4-amino-1-naphthalenesulfonic acid (22.33 g) and phenol(9.41 g) in water (73 ml) was added 20% aqueous sodium hydroxide (19.90g) and the resulting solution was adjusted to pH 8.1 with 0.1N aqueoussodium hydroxide. The weight of the solution was adjusted to 134.20 gwith water and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 7.5 hours under refluxing (1st step). The mixture was cooledto room temperature, adjusted to pH 11.0 with 20% aqueous sodiumhydroxide (-1.50 g) and refluxed for 1 hour (2nd step) to afford anaqueous solution of the condensate (162.10 g).

Ratio (4-amino-1-naphthalenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.61

Molecular weight: Mw: 2175

EXAMPLE 31

To a mixture of 4-aminobenzenesulfonic acid (303.1 g) and phenol (164.7g) in water (115 ml) was added 20% aqueous sodium hydroxide (357.0 g)and the mixture was stirred at 70° C. The resulting solution wasadjusted to pH 7.65 with 0.1N aqueous sodium hydroxide. The weight ofthe solution was adjusted to 990.7 g with water and then heated. To thesolution was added 37% aqueous formaldehyde (284.0 g) under refluxingand the reaction mixture was stirred for 2 hours under refluxing (1ststep). The mixture was cooled to room temperature, adjusted to pH 11.0with 20% aqueous sodium hydroxide (184.4 g) and refluxed for 1 hour (2ndstep) to afford an aqueous solution of the condensate (1459.1 g).

Ratio (4-aminobenzenesulfonic acid:phenol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:0.98

Molecular weight: Mw: 3572, Mn: 918

Examples 32 to 35 was conducted in a similar manner to that of Example31.

    __________________________________________________________________________                                  Polymerizing conditions                         Stating monomers              1st step 2nd step Resulting condensate          Example                                                                            Ratio (4-aminobenzenesulfonic                                                                 Ratio (starting                                                                        Initial                                                                           Reaction                                                                           Initial                                                                           Reaction   Molecular weight        No.  acid:phenol:formaldehyde)                                                                     monomers:water)                                                                        pH  time pH  time Viscosity                                                                           Mw   Mn                 __________________________________________________________________________    32   0.8:1.2:2.2     1:0.99   7.65                                                                              2.0  11.0                                                                              1.0  27.2  4513                    33   0.8:1.2:2.4     1:0.97   7.65                                                                              2.0  11.0                                                                              1.0  17.1  4223                    34   1.2:0.8:2       1:0.96   7.65                                                                              2.0  11.0                                                                              1.0  5.4                           35   1:1:1.8         1:1.00   7.65                                                                              2.0  11.0                                                                              1.0  7.2   4676 834                __________________________________________________________________________

EXAMPLE 36

To a mixture of 4-aminobenzenesulfonic acid (17.32 g) and m-cresol(10.80 g) in water (173.2 ml) was added 20% aqueous sodium hydroxide(20.45 g) and the mixture was stirred at 85° C. The resulting solutionwas adjusted to pH 7.42 with 0.1N aqueous sodium hydroxide and thenheated. To the solution was added 37% aqueous formaldehyde (16.23 g)under refluxing and the reaction mixture was stirred for 7.5 hours underrefluxing (1st step). The mixture was cooled to room temperature,adjusted to pH 11.0 with 20% aqueous sodium hydroxide (2.87 g) andrefluxed for 3 hours (2nd step) to afford an aqueous solution of thecondensate (240.90 g).

Ratio (4-aminobenzenesulfonic acid:m-cresol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:5.23

Viscosity of the aqueous solution of the condensate: 8.8 (cP at 25° C.,30%)

Molecular weight: Mw: 8981, Mn: 858

EXAMPLE 37

To a mixture of 3-aminobenzenesulfonic acid (17.32 g) and salicylic acid(13.80 g) in water (52 ml) was added 20% aqueous sodium hydroxide (40.60g) and the resulting solution was adjusted to pH 8.20 with 0.1N aqueoussodium hydroxide. The weight of the solution was adjusted to 131.30 gwith water and then heated. To the solution was added 37% aqueousformaldehyde (16.23 g) under refluxing and the reaction mixture wasstirred for 7.5 hours under refluxing (1st step). The mixture was cooledto room temperature, adjusted to pH 11.2 with 20% aqueous sodiumhydroxide (1.03 g) and refluxed for 3 hours (2nd step) to afford anaqueous solution of the condensate (148.60 g).

Ratio (3-aminobenzenesulfonic acid:salicylic acid: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.26

Viscosity of the aqueous solution of the condensate: 4.1 (cP at 25° C.,21.5%)

Molecular weight: Mw: 1110, Mn: 562

EXAMPLE 38

To a mixture of 4-aminobenzenesulfonic acid (8.65 g) and guaiacol (6.20g) in water (117.3 ml) was added 20% aqueous sodium hydroxide (10.24 g)and the mixture was stirred at 80° C. The resulting solution wasadjusted to pH 7.51 with 0.1N aqueous sodium hydroxide and then heated.To the solution was added 37% aqueous formaldehyde (8.12 g) underrefluxing and the reaction mixture was stirred for 7.5 hours underrefluxing (1st step). The mixture was cooled to room temperature,adjusted to pH 11.0 with 20% aqueous sodium hydroxide (9.39 g) andrefluxed for 3 hours (2nd step) to afford an aqueous solution of thecondensate (93.30 g).

Ratio (4-aminobenzenesulfonic acid:guaiacol: formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:6.56

Viscosity of the aqueous solution of the condensate: 9.3 (cP at 25° C.,30%)

Molecular weight: Mw: 1215, Mn: 432

EXAMPLE 39

To a mixture of 4-aminobenzenesulfonic acid (8.65 g) and salicylic acid(6.91 g) in water (24 ml) was added 20% aqueous sodium hydroxide (20.12g) and the mixture was stirred at 75° C. The resulting solution wasadjusted to pH 7.58 with 0.1N aqueous sodium hydroxide. The weight ofthe solution was adjusted to 73.80 g with water and then heated. To thesolution was added 37% aqueous formaldehyde (8.12 g) under refluxing andthe reaction mixture was stirred for 7.5 hours under refluxing (1ststep). The mixture was cooled to room temperature, adjusted to pH 11.0with 20% aqueous sodium hydroxide and refluxed for 3 hours (2nd step) toafford an aqueous solution of the condensate.

Ratio (4-aminobenzenesulfonic acid:salicylic acid:formaldehyde): 1:1:2

Ratio (starting monomers:water): 1:2.27

Viscosity of the aqueous solution of the condensate: 5.7 (cP at 25° C.,30%)

Molecular weight: Mw: 1464, Mn: 552

What we claim is:
 1. A fresh cementing composition having good fluiditywhich comprises fresh inorganic hydraulic cement and anaminoarylsulfonic acid-phenol-formaldehyde condensate prepared bypolymerizing 20 to 70 parts by weight of a compound of the generalformula

    R.sup.1 SO.sub.3 H                                         (I)

wherein R¹ is ##STR4## (wherein R_(a) ¹ is hydrogen or lower alkyl) or##STR5## or its salt, 10 to 50 parts by weight of a compound of thegeneral formula: ##STR6## wherein R² is hydrogen, lower alkyl, loweralkoxy or hydroxy or its salt, and 10 to 40 parts by weight offormaldehyde.
 2. A fresh cementing composition having good fluidity,which comprises fresh inorganic hydraulic cement and anaminoarylsulfonic acid-phenol-formaldehyde condensate prepared bypolymerizing 20 to 70 parts by weight of 4-aminobenzenesulfonic acid, 10to 50 parts by weight of phenol and 10 to 40 parts by weight offormaldehyde.
 3. A fresh concrete composition having good fluidity,which comprises fresh concrete and an aminoarylsulfonicacid-phenol-formaldehyde condensate prepared by polymerizing 70 parts byweight of a compound of the general formula:

    R.sup.1 SO.sub.3 H                                         (I)

wherein R¹ is ##STR7## (wherein R_(a) ¹ is hydrogen or lower alkyl) or##STR8## or its salt, 10 to 50 parts by weight of a compound of thegeneral formula: ##STR9## wherein R² is hydrogen, lower alkyl, loweralkoxy or hydroxy or its salt, and 10 to 40 parts by weight offormaldehyde.
 4. A fresh concrete composition having good fluidity,which comprises fresh concrete and an aminoarylsulfonicacid-phenol-formaldehyde condensate prepared by polymerizing 20 to 70parts by weight of 4-aminobenzenesulfonic acid, 10 to 50 parts by weightof phenol and 10 to 40 parts by weight of formaldehyde.
 5. The cementcomposition of claim 1 wherein the fresh cement is portland cement. 6.The cement composition of claim 2 wherein the fresh cement is portlandcement.
 7. The concrete composition of claim 3 wherein the freshconcrete composition comprises portland cement.
 8. The concretecomposition of claim 4 wherein the fresh concrete comprises portlandcement.